Back contact for a photovoltaic module

ABSTRACT

The present invention relates to photovoltaic modules and methods of manufacturing photovoltaic modules.

CLAIM OF PRIORITY

This application is a continuation of U.S. patent application Ser. No.13/183,209, filed Jul. 14, 2011, which claims priority under 35 U.S.C.§119(e) to U.S. Provisional Patent Application Ser. No. 61/364,664 filedon Jul. 15, 2010, which are hereby incorporated by reference in theirentireties.

TECHNICAL FIELD

The present invention relates to photovoltaic modules and methods ofmanufacturing photovoltaic modules.

BACKGROUND

A photovoltaic device may include a semiconductor material depositedover a substrate. The semiconductor may contain a first layer serving asa window layer and a second layer serving as an absorber layer. Thesemiconductor window layer may allow solar radiation to reach theabsorber layer, and the absorber layer, which may contain cadmiumtelluride, may convert the solar radiation to electricity. Thephotovoltaic device may also include a back contact to facilitateconnectivity. However, the back contact contributes electricalresistance to the photovoltaic device which reduces the device's overallefficiency.

DESCRIPTION OF DRAWINGS

FIG. 1 is a side view of a photovoltaic device.

FIG. 2 is a side view of a transparent conductive oxide stack.

FIG. 3 is a side view of a back contact.

FIG. 4 is a method of manufacturing a photovoltaic device.

FIG. 5 is a method of manufacturing a back contact layer for aphotovoltaic device.

FIG. 6 is a method of manufacturing a back contact layer for aphotovoltaic device.

FIG. 7 is a method of manufacturing a back contact layer for aphotovoltaic device.

FIG. 8 is a method of manufacturing a back contact layer for aphotovoltaic device.

FIG. 9 is a method of manufacturing a back contact layer for aphotovoltaic device.

DETAILED DESCRIPTION

A photovoltaic device may include an optically transparent substrate, atransparent conductive oxide layer adjacent to the substrate, and asemiconductor material adjacent to the transparent conductive oxidelayer. In addition, one or more metal layers may be deposited on a backsurface of the semiconductor material to form a back contact. With thetransparent conductive oxide layer acting as a front contact, the frontand back contacts may serve as electrodes for transportingphoto-generated current away from the photovoltaic device.

The layers of semiconductor material may include a bi-layer, which mayinclude an n-type semiconductor window layer, and a p-type semiconductorabsorber layer. The n-type window layer and the p-type absorber layermay be positioned in contact with one another to form a p-n junction. Asa result of diffusion across the junction, negative acceptor ions areformed on the p-type side and positive donor ions are formed on then-type side. The presence of the ions creates a built-in electric fieldacross the junction. When a photon is absorbed within the p-n junction,an electron hole pair is formed. The electrons are then swept towardsthe n-type layer and holes are swept towards the p-type layer. Electronscan then flow back to the p-type side via an external current path. Theresulting electron flow provides current, which combined with theresulting voltage from the electric field, creates power. The result isa conversion of photon energy into electrical power.

The transparent conductive oxide layer may be deposited between thesubstrate and the semiconductor bi-layer to serve as a front contact.The transparent conductive oxide layer may include, for example, cadmiumstannate, since it exhibits high optical transmission and low electricalresistance. The transparent conductive oxide may be part of athree-layer stack. For instance, the transparent conductive oxide stackmay include a barrier layer, a transparent conductive oxide layer, and abuffer layer. The buffer layer may be included between the transparentconductive oxide layer and the semiconductor window layer to decreasethe likelihood of irregularities occurring during the formation of thesemiconductor window layer. Also, the barrier layer can be incorporatedbetween the substrate and the transparent conductive oxide layer tolessen diffusion of sodium or other contaminants from the substrate tothe semiconductor layers, which could result in poor performance anddegradation of the photovoltaic devices. The barrier layer may include,for example, silicon dioxide.

The back contact layer may transport electrical charge away from thedevice and may include one or more metal layers deposited adjacent tothe semiconductor absorber layer. In particular, the back contact mayinclude a first metal layer deposited adjacent to the semiconductorabsorber layer. The first metal layer may be deposited using anysuitable process or combination of processes. For instance, the firstmetal layer may be deposited by physical vapor deposition techniquessuch as magnetron sputtering, thermal evaporation or laser ablation.Alternate methods of depositing a first layer may include chemical vapordeposition, wet methods such as electrochemical or electrolessdeposition, or even mechanical roll coating. After the first metal layeris deposited, it may be heat treated to alter its physical andelectrical properties. During the deposition process, nitrogen may beintroduced into the back contact metal to improve the overall efficiencyof the photovoltaic device. The second metal layer may be deposited byphysical vapor deposition, electrochemical or electroless deposition,chemical vapor deposition, mechanical roll coating, or a combinationthereof.

A variety of materials are available for the first and second metallayers, including molybdenum, aluminum, chromium, iron, nickel,titanium, vanadium, manganese, cobalt, zinc, ruthenium, tungsten,silver, gold, copper, mercury tellurium, titanium disilicide, titaniumsilicide, molybdenum nitride, titanium nitride, tungsten nitride andplatinum. Molybdenum nitride functions particularly well as a backcontact metal due to its relative stability at processing temperaturesand low contact resistance. Similarly, silver, gold, and copper functionwell as back contact metals since they are low-resistance electricalconductors.

The heat treating process may include annealing or any other suitableheat treating process. Post-deposition annealing of the first metallayer may relieve stress as well as induce desirable reactions betweenthe metal and the semiconductor layer. Post-deposition annealing mayalso transform the metal layer to form a desirable metallurgical phase.For instance, annealing may reduce the contact resistance of the firstmetal layer. Contact resistance is defined as a contribution to thetotal resistance of a device resulting from electrical leads andconnections. By reducing the contact resistance, the overall efficiencyof the photovoltaic device may be increased.

When heat treating the back contact, high temperatures may be desirableto cause inter-diffusion between the semiconductor absorber layer andthe first metal layer. High temperatures may also be desirable totransform the first metal layer to a desired phase. However, to preventdopant redistribution, the thermal budget should be carefullycontrolled. Thermal budget is defined as the cumulative thermal energyimparted to the photovoltaic panel by all thermal processing stepsduring manufacturing. If high temperatures are required duringmanufacturing, a moderate thermal budget may be achieved by limiting theduration of the process. Similarly, if a process requires significanttime to complete, the temperature must be reduced to avoid an excessivethermal budget.

While a high temperature may be desirable when forming the first metallayer of the back contact, the temperature must be controlled to avoidreducing the integrity of the photovoltaic device. In particular, thelayers of metal used to create the back contact may have coefficients ofthermal expansion that differ from those of the semiconductor, TCO, andsubstrate layers. Adding heat to layers having differing coefficients ofthermal expansion may induce strain that can result in cracking or evengross delamination of the layers. Accordingly, excessive heat treatmenttemperatures and durations should be avoided.

To produce a reliable back contact, the semiconductor surface should beextremely clean prior to forming the back contact layer adjacent to thesemiconductor surface. Under certain conditions, unwanted oxides mayform on the semiconductor surface. Before a first metal layer can bedeposited on the semiconductor, the oxides must be removed. Surfacecleaning may be performed by sputter-etching, chemical etching, reactivegas etching, ion milling, or any other suitable process.

In one aspect, a photovoltaic module may include a substrate, atransparent conductive oxide layer adjacent to the substrate, asemiconductor layer adjacent to the transparent conductive oxide layer,and a back contact layer adjacent to the semiconductor layer. The backcontact layer may include a first metal layer formed adjacent to thesubstrate layer and a second metal layer foamed adjacent to the firstmetal layer. In particular, the first metal layer may include a materialselected from the group consisting of molybdenum, tungsten, nickel,cobalt, titanium, molybdenum nitride, titanium nitride, tungsten nitrideand mercury tellurium. The first metal layer may be heat treated at atemperature of about 100 C to about 400 C for a duration of about 30seconds to about 30 minutes. Preferably, the first metal layer may beheat treated at a temperature of about 200 C to about 300 C for aduration of about 1 minute to about 20 minutes. The first metal layermay have a thickness of about 5 angstroms to about 300 angstroms.Preferably, the first metal layer may have a thickness of about 50angstroms to about 250 angstroms. The second metal layer may include amaterial selected from the group consisting of silver, gold, copper, andaluminum and may be heat treated at a temperature of about 50 C to about400 C for a duration of about 1 minute to about 30 minutes. Preferably,the second metal layer may be heat treated at a temperature of about 50C to about 150 C for a duration of about 5 minutes to about 20 minutes.The second metal layer may have a thickness of about 500 angstroms toabout 10000 angstroms. Preferably, the second metal layer may have athickness of about 1000 angstroms to about 5000 angstroms.

In another aspect, a method of manufacturing a photovoltaic device mayinclude providing a substrate, forming a transparent conductive oxidelayer adjacent to the substrate, forming a semiconductor layer adjacentto the transparent conductive oxide layer, and forming a back contactlayer adjacent to the semiconductor layer. The step of forming a backcontact layer may include forming a first metal layer adjacent to thesubstrate layer, heat treating the first metal layer, and forming asecond metal layer adjacent to the first metal layer. The first metallayer may include a material selected from the group consisting ofmolybdenum, tungsten, nickel, cobalt, titanium, molybdenum nitride,titanium nitride, tungsten nitride, and mercury tellurium. The step ofheat treating the first metal layer may include a temperature of about100 C to about 400 C for a duration of about 30 seconds to about 30minutes. Preferably, the heat treating process may occur at atemperature of about 200 C to about 300 C for a duration of about 1minute to about 20 minutes. The first metal layer may have a thicknessof about 5 angstroms to about 300 angstroms. Preferably, the first metallayer may have a thickness of about 50 angstroms to about 250 angstroms.The step of forming a back contact may include applying a second metallayer. The second metal layer may include a material selected from thegroup consisting of silver, gold, copper, and aluminum. The second metallayer may have a thickness of about 500 angstroms to about 10000angstroms. Preferably, the second metal layer may have a thickness ofabout 1000 angstroms to about 5000 angstroms. The second metal layer mayor may not require the application of a thermal treatment.

In another aspect, a photovoltaic module can include a plurality ofphotovoltaic cells adjacent to a substrate and a back cover adjacent tothe plurality of photovoltaic cells. Each one of the plurality ofphotovoltaic cells can include a transparent conductive oxide layeradjacent to the substrate, a semiconductor layer adjacent to thetransparent conductive oxide layer, and a back contact layer adjacent tothe semiconductor layer. The back contact layer can include a firstmetal layer formed adjacent to the semiconductor layer and a secondmetal layer formed adjacent to the first metal layer.

The first metal layer can include a material including molybdenum,tungsten, nickel, cobalt, titanium, molybdenum nitride, titaniumnitride, tungsten nitride, or mercury tellurium. The first metal layercan have a thickness of about 5 angstroms to about 300 angstroms. Thesecond metal layer can include a material selected from the groupconsisting of silver, gold, copper, and aluminum The second metal layercan have a thickness of about 500 angstroms to about 10000 angstroms.

In another aspect, a method for generating electricity can includeilluminating a photovoltaic cell with a beam of light to generate aphotocurrent and collecting the generated photocurrent. The photovoltaiccell can include a substrate, a transparent conductive oxide layeradjacent to the substrate, a semiconductor layer adjacent to thetransparent conductive oxide layer, and a back contact layer adjacent tothe semiconductor layer. The back contact layer can include a firstmetal layer formed adjacent to the semiconductor layer a second metallayer formed adjacent to the first metal layer.

As shown in FIG. 1, a photovoltaic device 100 may include a substrate105, a transparent conductive oxide stack 110, a semiconductor bi-layerincluding a semiconductor window layer 115 and a semiconductor absorberlayer 120, a back contact layer 125, and a back support 130. Thesubstrate 105 may include an optically transparent material, such assoda-lime glass. However, since the primary function of the substrate105 is to protect the device from physical damage caused by moisture ordebris while permitting penetration of solar radiation, any suitabletransparent material may be used. Similar to the substrate 105, the backsupport 130 may serve to protect and enclose the photovoltaic device100. The back support 130 may be any suitable material, such assoda-lime glass.

As shown in FIG. 2, a transparent conductive oxide stack 110 may includea barrier layer 205, a transparent conductive oxide layer 210, and abuffer layer 215. The barrier layer 205 may be formed adjacent to thesubstrate 105. One or more barrier layers 205 may include any suitablematerial, including, for example, a silicon oxide, aluminum-dopedsilicon oxide, boron-doped silicon oxide, phosphorous-doped siliconoxide, silicon nitride, aluminum-doped silicon nitride, boron-dopedsilicon nitride, phosphorous-doped silicon nitride, siliconoxide-nitride, titanium oxide, niobium oxide, tantalum oxide, aluminumoxide, zirconium oxide, tin oxide, or combinations thereof. Thetransparent conductive oxide layer 210 may be formed adjacent to thebarrier layer 205 and may include any suitable material. For instance,the transparent conductive oxide layer 210 may include cadmium stannate.Alternately, the transparent conductive oxide layer 210 may include anysuitable material or materials. For instance, the transparent conductiveoxide layer 210 may include a layer of cadmium and tin and may be anysuitable thickness. The transparent conductive oxide layer 210 may havea thickness ranging from, for example, 100 to 1000 nm. The transparentconductive oxide stack 110 may also include a buffer layer 215 which maybe formed adjacent to the transparent conductive oxide layer 210. Thepresence of the buffer layer 215 during manufacturing may decrease thelikelihood of irregularities occurring during the formation of thesemiconductor window layer 115. The transparent conductive oxide stack110 may be manufactured using a variety of deposition techniques,including, for example, low pressure chemical vapor deposition,atmospheric pressure chemical vapor deposition, plasma-enhanced chemicalvapor deposition, thermal chemical vapor deposition, DC or ACsputtering, spin-on deposition, or spray-pyrolysis. Each depositionlayer can be of any suitable thickness, for example, in the range ofabout 10 to about 5000 angstroms.

The semiconductor window layer 115 may be formed adjacent to thetransparent conductive oxide stack 110. The semiconductor absorber layer120 may formed adjacent to the semiconductor window layer 115. Together,the semiconductor window layer 115 and the semiconductor absorber layer120 form a semiconductor bi-layer. The semiconductor bi-layer mayinclude cadmium telluride (CdTe). Alternately, the semiconductorbi-layer may include any suitable compound, such as copper indiumgallium selenide (CIGS). The window layer 115 may be an n-typesemiconductor window layer, and the absorber layer 120 may be a p-typesemiconductor absorber layer. The n-type window layer 115 and the p-typeabsorber layer 120 may be positioned in contact with one another tocreate an electric field.

The back contact layer 125 may be formed adjacent to the semiconductorabsorber layer 120. The back contact layer 125 may cover a portion or anentire surface of the semiconductor absorber layer 120. As shown in FIG.3, the back contact layer 125 may include a first metal layer 305 and asecond metal layer 310. The first metal layer may be adjacent to thesemiconductor absorber layer 120, and the second metal layer 310 may beadjacent to the first metal layer 305. The first metal layer 305 mayinclude a material selected from the group consisting of molybdenum,aluminum, chromium, iron, nickel, titanium, vanadium, manganese, cobalt,zinc, ruthenium, tungsten, silver, gold, copper, mercury tellurium,titanium disilicide, titanium silicide, molybdenum nitride, titaniumnitride, tungsten nitride, and platinum or a combination thereof.Alternately, any suitable material may be used. The first metal layer305 may have a thickness ranging from 5 angstroms to 300 angstroms.Preferably, the first metal layer may have a thickness ranging from 50to 250 angstroms.

The first metal layer 305 may be heat treated to alter, for instance,its electrical and mechanical properties. The heat treating of the firstmetal layer 305 may include annealing and may result in the formation ofan ohmic contact between, for example, the cadmium telluridesemiconductor and the first metal layer 305. The annealing may occur inthe presence of a gas such as, for example, nitrogen gas selected tocontrol the atmosphere of the annealing process. The annealing may beaided by providing an oxygen-depleting or oxygen-reducing environment.The first metal layer 305 may be annealed under any suitable pressure,for example, under reduced pressure at about 0.01 Pa (10−4 Torr). Also,the first metal layer 305 may be annealed at any suitable temperature ortemperature range. For example, the first metal layer 305 may beannealed at about 100 to about 400 C. Preferably, the first metal layer305 may be annealed at about 200 to about 300 C. In addition, the firstmetal layer 305 may be annealed for any suitable duration. For example,the first metal layer 305 may be annealed for a duration ranging fromabout 30 seconds to about 30 minutes. Preferably, the first metal layer305 may be annealed for a duration ranging from about 1 minute to about20 minutes. By annealing the first metal layer 305 at a hightemperature, inter-diffusion may occur between the semiconductorabsorber layer 120 and the first metal layer 305. The first metal layer305 may be transformed into a metallurgical phase that affords lowcontact resistance to the semiconductor absorber layer 120. Theselection of temperature and duration values must account for thephysical limitations and properties of the various layers of the device100. For instance, the thermal budget must be large enough to cause areduction in contact resistance of the first metal layer 305, but thethermal budget must also be small enough to avoid degrading the otherlayers (e.g. 110,115, 120).

Once the first metal layer 305 is deposited adjacent the semiconductorabsorber layer 120, a second metal layer 310 may be deposited on thefirst metal layer 305. The second metal layer 310 may include a materialselected from the group consisting of molybdenum, aluminum, chromium,iron, nickel, titanium, vanadium, manganese, cobalt, zinc, ruthenium,tungsten, silver, gold, copper, mercury tellurium, titanium disilicide,titanium silicide, molybdenum nitride, titanium nitride, tungstennitride, and platinum or a combination thereof. Alternately, anysuitable material may be used. Similar to the first metal layer, thesecond metal layer 310 may be heat treated to improve its electrical andmechanical properties. In particular, the second metal layer 310 may beheat treated to improve adhesion to the first metal layer 305 and toreduce its electrical resistance. For instance, an annealing process mayrefine the microstructure of the second metal layer to improve itscurrent carrying ability. The choice of temperature and duration valuesfor the heat treatment process may be limited by the existing layers(e.g. 110, 115, 120, and 305). For instance, the temperature andduration values must be low enough to avoid degrading the existinglayers or causing detrimental interactions amongst the layers (e.g. 110,115, 120, and 305). Alternately, the heat treatment process may beomitted if the second metal layer 310 exhibits desirable physical andelectrical properties.

As shown in FIG. 4, a method of manufacturing a photovoltaic device 100may include providing a substrate 405, forming a transparent conductiveoxide layer adjacent to the substrate 410, forming a semiconductor layeradjacent to the transparent conductive oxide 415, and forming a backcontact layer 420 adjacent to the semiconductor layer. Forming a backcontact layer 420 may be accomplished through methods described in FIGS.5-10. In particular, as shown in FIG. 5, forming a back contact layermay include forming a first metal layer adjacent to the firstsemiconductor layer 505, heat treating the first metal layer 510, andforming a second metal layer adjacent to the first metal layer 515. Asshown in FIG. 6, the method of FIG. 5 may include an additional step ofheat treating the second metal layer 620. This step can be achieved byusing an established technique like microwave heating to selectivelyheat a given layer. Alternately, as shown in FIG. 7, the method of FIG.5 may include an additional step of heat treating both the first andsecond metal layers 720.

Once the first metal layer 305 is deposited adjacent to thesemiconductor absorber layer 120, a passivating layer (not shown) may bedeposited adjacent the first layer 305. The passivating layer may capthe first metal layer 305 and protect against oxidation and grainboundary grooving prior to, during, and after the heat treating process.The passivating layer may be any suitable material. The passivatinglayer may be incorporated into the back contact layer, or it may bestripped via dry etching, wet chemical, or any other suitable processprior to forming the second metal layer 310. For example, as shown inFIG. 8, the method may include forming a first metal layer adjacent tothe semiconductor layer 805, forming a passivating layer adjacent to thefirst metal layer 810, heat treating the first metal layer 815, removingthe passivating layer 820, and forming a second metal layer adjacent tothe first metal layer 825. The second metal layer may then be heattreated in a subsequent step. In addition, the step of removing thepassivating layer may omitted as shown in the method of FIG. 9. In thisway, the passivating layer may become a permanent component of the backcontact layer.

Although the steps in the aforementioned methods are shown in particularorders in FIGS. 5-9, this is not limiting. For instance, the formingsteps and heat treating steps may occur prior to forming the backcontact layer adjacent to the semiconductor layer. Although only twolayers are shown, the back contact layer 125 may include two or morelayers. For instance, the back contact layer 125 may include two, three,four, five, or six layers. The additional layers may be formed insequential steps similar to the two-part back contact described herein.The additional layers may be heat treated as described herein to improvetheir electrical and mechanical properties. In addition, subsequentlayers may be formed and heat treated separately from the photovoltaicdevice to avoid high thermal budgets from adversely affecting thesemiconductor bi-layer.

Details of one or more embodiments are set forth in the accompanyingdrawings and description. Other features, objects, and advantages willbe apparent from the description, drawings, and claims. Although anumber of embodiments of the invention have been described, it will beunderstood that various modifications may be made without departing fromthe spirit and scope of the invention. It should also be understood thatthe appended drawings are not necessarily to scale, presenting asomewhat simplified representation of various features illustrative ofthe basic principles of the invention.

What is claimed is:
 1. A method for manufacturing a back contact for aphotovoltaic module, the method comprising: forming a semiconductorwindow layer over a substrate; forming a semiconductor absorber layerover the window layer, the semiconductor absorber layer comprising oneof CdTe and CIGS; removing oxides from the absorber layer surface;forming a first metal layer in direct physical contact with the oxideremoved surface of the absorber layer, the first metal layer comprisinga material selected from the group consisting of molybdenum, tungsten,nickel, cobalt, titanium, molybdenum nitride, titanium nitride, tungstennitride, mercury tellurium, or any combination thereof; heat treatingthe first metal layer; and forming a second metal layer adjacent to thefirst metal layer.
 2. The method of claim 1, wherein the first metallayer comprises a material selected from the group consisting ofmolybdenum, molybdenum nitride, or any combination thereof.
 3. Themethod of claim 1, wherein the step of heat treating the first metallayer comprises a temperature of about 100° C. to about 400° C. and aduration of about 30 seconds to about 30 minutes.
 4. The method of claim1, wherein the step of heat treating the first metal layer comprises atemperature of about 200° C. to about 300° C. and a duration of about 1minute to about 20 minutes.
 5. The method of claim 1, wherein the firstmetal layer has a thickness of about 5 angstroms to about 300 angstroms.6. The method of claim 1, wherein the first metal layer has a thicknessof about 50 angstroms to about 250 angstroms.
 7. The method of claim 1,wherein the second metal layer comprises a material selected from thegroup consisting of aluminum, chromium, iron, vanadium, manganese, zinc,ruthenium, silver, gold, copper, platinum, tungsten, nickel, cobalt,titanium, molybdenum nitride, titanium disilicide, titanium silicide,titanium nitride, tungsten nitride, and mercury tellurium, or anycombination thereof.
 8. The method of claim 1, wherein the step offorming a back contact layer further comprises heat treating the secondmetal layer at a temperature of about 50° C. to about 400° C. for aduration of about 1 minute to about 30 minutes.
 9. The method of claim1, wherein the step of forming a back contact layer further comprisesheat treating the second metal layer at a temperature of about 50° C. toabout 150° C. for a duration of about 5 minutes to about 20 minutes. 10.The method of claim 1, wherein the second metal layer has a thickness ofabout 500 angstroms to about 10000 angstroms.
 11. The method of claim 1,wherein the second metal layer has a thickness of about 1000 angstromsto about 5000 angstroms.
 12. The method of claim 1, further comprising:cleaning a surface of the formed first metal layer before forming thesecond metal layer